EP2666184A1 - Interface améliorée entre une couche de matériau à base d'éléments des groupes i-iii-vi2 et un substrat en molybdène - Google Patents

Interface améliorée entre une couche de matériau à base d'éléments des groupes i-iii-vi2 et un substrat en molybdène

Info

Publication number
EP2666184A1
EP2666184A1 EP11797018.6A EP11797018A EP2666184A1 EP 2666184 A1 EP2666184 A1 EP 2666184A1 EP 11797018 A EP11797018 A EP 11797018A EP 2666184 A1 EP2666184 A1 EP 2666184A1
Authority
EP
European Patent Office
Prior art keywords
layer
iii
copper
adaptation layer
adaptation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
EP11797018.6A
Other languages
German (de)
English (en)
Other versions
EP2666184B1 (fr
Inventor
Pierre-Philippe Grand
Jesus Salvador Jaime Ferrer
Emmanuel Roche
Hariklia Deligianni
Raman Vaidyanathan
Kathleen B. Reuter
Qiang Huang
Lubomyr Romankiw
Maurice Mason
Donna S. Zupanski-Nielsen
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Electricite de France SA
Original Assignee
Nexcis SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Nexcis SAS filed Critical Nexcis SAS
Priority to EP11797018.6A priority Critical patent/EP2666184B1/fr
Publication of EP2666184A1 publication Critical patent/EP2666184A1/fr
Application granted granted Critical
Publication of EP2666184B1 publication Critical patent/EP2666184B1/fr
Active legal-status Critical Current
Anticipated expiration legal-status Critical

Links

Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/04—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer
    • H01L21/18—Manufacture or treatment of semiconductor devices or of parts thereof the devices having potential barriers, e.g. a PN junction, depletion layer or carrier concentration layer the devices having semiconductor bodies comprising elements of Group IV of the Periodic Table or AIIIBV compounds with or without impurities, e.g. doping materials
    • H01L21/20—Deposition of semiconductor materials on a substrate, e.g. epitaxial growth solid phase epitaxy
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02367—Substrates
    • H01L21/0237—Materials
    • H01L21/02422—Non-crystalline insulating materials, e.g. glass, polymers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/18—Processes or apparatus specially adapted for the manufacture or treatment of these devices or of parts thereof
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02436—Intermediate layers between substrates and deposited layers
    • H01L21/02439—Materials
    • H01L21/02491—Conductive materials
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02518—Deposited layers
    • H01L21/02521—Materials
    • H01L21/02568—Chalcogenide semiconducting materials not being oxides, e.g. ternary compounds
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L21/00—Processes or apparatus adapted for the manufacture or treatment of semiconductor or solid state devices or of parts thereof
    • H01L21/02—Manufacture or treatment of semiconductor devices or of parts thereof
    • H01L21/02104—Forming layers
    • H01L21/02365—Forming inorganic semiconducting materials on a substrate
    • H01L21/02612—Formation types
    • H01L21/02614—Transformation of metal, e.g. oxidation, nitridation
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01L—SEMICONDUCTOR DEVICES NOT COVERED BY CLASS H10
    • H01L31/00—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof
    • H01L31/0248—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies
    • H01L31/0256—Semiconductor devices sensitive to infrared radiation, light, electromagnetic radiation of shorter wavelength or corpuscular radiation and specially adapted either for the conversion of the energy of such radiation into electrical energy or for the control of electrical energy by such radiation; Processes or apparatus specially adapted for the manufacture or treatment thereof or of parts thereof; Details thereof characterised by their semiconductor bodies characterised by the material
    • H01L31/0264—Inorganic materials
    • H01L31/032—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312
    • H01L31/0322—Inorganic materials including, apart from doping materials or other impurities, only compounds not provided for in groups H01L31/0272 - H01L31/0312 comprising only AIBIIICVI chalcopyrite compounds, e.g. Cu In Se2, Cu Ga Se2, Cu In Ga Se2
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E10/00—Energy generation through renewable energy sources
    • Y02E10/50—Photovoltaic [PV] energy
    • Y02E10/541—CuInSe2 material PV cells

Definitions

  • the invention relates to the domain of manufacturing in thin layers I-III-VI compounds, for example for photovoltaic applications.
  • the element I from the first group of the periodic table of the elements can be copper (or also silver, or even a mixture of these elements),
  • the element III from the third group can be indium, gallium, aluminum or a mixture of these elements, and
  • the element VI from the sixth group can be selenium, sulfur or a mixture of these elements.
  • Such a compound globally has a chalcopyrite type crystallographic structure.
  • This compound in particular has excellent photovoltaic properties. It can be then integrated in active, thin layer form in photovoltaic cells, in particular in solar panels.
  • a non-expansive technique for depositing such a thin layer on large substrates involves often a chemical deposition and, more particularly, a deposition by electrolysis.
  • the substrate for example a thin layer of molybdenum on glass
  • needing to receive the deposition of the thin layer is provided on the surface of an electrode immersed in an electrolytic bath composing salts of element I and/or element III and/or element VI.
  • a voltage is applied to the electrode (relative to a reference mercury sulfate electrode) to initiate the deposition.
  • the process for manufacturing the whole solar cell product can further include steps of deposition of additional layers (such as a transparent ZnO layer, contact layers, etc.).
  • additional layers such as a transparent ZnO layer, contact layers, etc.
  • the solar cells based on the so-called “CIGS” material (“CIGS” for Copper (Cu), Indium (In) and/or Gallium (Ga), and Sulfur (S) and/or Selenium (Se))
  • CIGS for Copper (Cu), Indium (In) and/or Gallium (Ga), and Sulfur (S) and/or Selenium (Se)
  • a typical substrate is composed of a glass or a metal foil, and at least one conductive layer deposited on its surface.
  • the most common conductive layer used in the prior art is the molybdenum (Mo).
  • element VI S and/or Se
  • element VI can be added to one or several layers of I-III material thanks to a heating treatment in sulfur and/or selenium atmosphere, for obtaining a layer having the desired stoichiometry I-III- VI 2 .
  • This step is called “sulfuration” or “selenization” hereafter.
  • I-III- VI 2 (or I-III) layers One of the major issues observed in the prior art for the processes involving electrodeposition of I-III- VI 2 (or I-III) layers is the lack of adhesion between the Mo substrate and such layers. The lack of adhesion strongly decreases the electron collect at the back contact and thus reduces the performance of the solar cells.
  • the molybdenum substrate surface shows patchy oxide at certain locations and therefore the electroplated Cu-In-Ga (S-Se) layer on top does not adhere well in those areas where the molybdenum is oxidized.
  • an embodiment of the prior art for manufacturing a CuInS 2 layer can consist on:
  • MoO x molybdenum oxide
  • Cu x S copper sulfite compounds
  • the present invention aims to improve the situation. To that end, the invention proposes a method for fabricating a thin layer made of a I- III- VI alloy and having photovoltaic properties,
  • element I being Copper
  • element III being Indium and/or Gallium
  • element VI being Sulfur and/or Selenium
  • the method comprising first steps of:
  • said adaptation layer is deposited under near vacuum conditions and step b) comprises a first operation of depositing a first layer of I and/or III elements, under same conditions as the deposition of the adaptation layer, without exposing to air said adaptation layer.
  • step b) comprises then a second operation of depositing at least one second layer of I an/or III elements, by electrolysis.
  • said first and second layers comprise elements I and III and the method further comprises a step of:
  • step c) comprises an annealing operation in an atmosphere comprising at least one element VI. That kind of process is known as "sulfurization” or “selenization”.
  • the adaptation layer preferably comprises Molybdenum (or also Platinum as a variant).
  • the aforesaid first layer comprises Copper.
  • Its thickness is preferably greater than 40nm, while the adaptation layer has for example a thickness around 600nm.
  • the operation of depositing said second layer is performed in an acidic electrolysis bath.
  • the acidity of the bath can thus corrode oxidation formed of the seed layer itself.
  • the adaptation layer and the first layer can be deposited for example by sputtering and/or evaporation, preferably in a same machine.
  • said first and second layers comprise both Copper and Indium, and wherein the atomic ratio between the amount of Copper to Indium is thereby between 1 and 2.
  • An advantageous stoichiometry is for example Cunln 9 as commented below.
  • said first, second and third layers comprise both Copper, Indium, and Gallium, and the atomic ratios between the amounts of Copper to the sum of the amounts of Indium and Gallium is thereby between 0,6 and 2.
  • the present invention aims also at an electroplated I-III-VI compound layer deposited on a substrate through an adaptation layer,
  • element I being Copper
  • element III being Indium and/or Gallium
  • element VI being Sulfur and/or Selenium
  • adaptation layer and at least one layer comprising at least elements I and III are deposited under near vacuum conditions without exposing to air said adaptation layer, and wherein oxidation is reduced at the interface between the adaptation layer and the I-III-VI compound layer by a factor of at least 10, compared to a structure of an electroplated I-III-VI compound layer deposited on an adaptation layer without depositing said layer comprising at least elements I and III under near vacuum conditions.
  • the present invention aims also at a solar cell device comprising an electroplated I-III- VI compound layer according to the invention.
  • figure 1 schematically shows an electrolytic bath to grow layers by electro- deposition
  • figure 2 schematically shows the seed layer underneath a I-III electro-deposited layer
  • figure 3 is a diagram showing resistivity properties of a copper seed layer versus its thickness
  • figure 4 shows reflectance stability versus the copper seed layer thickness
  • figure 5 shows the effect of temperature control of the substrate when exposed to air after deposition of the seed layer, on its reflectance (relative to its oxidation)
  • figure 6 is a SIMS diagram (for "Secondary Ion Mass Spectroscopy") showing respective amounts of oxygen atoms in a molybdenum layer with a copper seed layer deposited on it (solid line) and without any seed layer (dashed line).
  • an electrolytic bath BA may include salts of element I and/or element III and/or element VI.
  • a voltage is applied to the electrode EL (relative to a reference mercury sulfate electrode ME) to initiate the deposition.
  • electrode EL relative to a reference mercury sulfate electrode ME
  • such baths are judged to be unstable because of the presence of the element VI in the bath.
  • growing a layer of global stoichiometry neighboring I-III for example and next treating the resulting layer by subsequent supply of element VI could be considered.
  • the growth of the I-III layer by electrolysis could turn out to be unstable and in particular the control of the stoichiometry of the I-III alloy in the final layer is not assured.
  • a multilayer structure according to a sequence of elementary layers (for example a layer of element I, then a layer of element III, and then optionally a new layer of element I and a layer of element III, etc.), and then apply a thermal treatment (typically annealing according to a selected sequence of raising, holding and lowering temperature) to obtain an "intermixed" structure, therefore mixed, of global I-III stoichiometry.
  • a thermal treatment typically annealing according to a selected sequence of raising, holding and lowering temperature
  • the element VI can be supplied subsequently (by thermal treatment of selenization and/or sulfuration) or at the same time as the aforementioned annealing to obtain the desired I-III- VT 2 stoichiometry.
  • the resulting layers have satisfactory photovoltaic properties by providing thereby good yields of photovoltaic cells incorporating such thin layers. More particularly, referring now to figure 2, such I-III layers are deposited on an adaptation layer Mo between the substrate SUB and the I-III layers CI.
  • the adaptation layer is generally made of a stable metallic material such as molybdenum.
  • the invention proposes to deposit a thin Cu, In or Ga "seed” layer or “strike” layer (referred as "SEED" on figure 2), on top of the adaptation layer Mo (made of molybdenum or of an alloy comprising that element for example).
  • This seed layer is deposited under vacuum or near vacuum conditions (for example by physical deposition technique (for example by spraying a target under very low pressure) or any equivalent technique).
  • Both the adaptation layer Mo and the seed layer SEED are deposited in "vacuum” conditions and in particular without exposure to air.
  • other possible I-III layers (referred as CI layers on figure 2) are deposited for example by electrolysis on the seed layer (which is electrically conductive since Cu, In and Ga are conductive metals).
  • an acid plating chemistry including salts of copper and/or indium and/or gallium and/or any other I, III material, is preferably used on top of the seed layer to etch possible oxide stains located on the top surface of the seed layer.
  • an acid plating chemistry including salts of copper and/or indium and/or gallium and/or any other I, III material, is preferably used on top of the seed layer to etch possible oxide stains located on the top surface of the seed layer.
  • most of the existing Cu, In, Ga electrolytic solutions for electrolysis are acid. Tests have been carried out with a copper layer as a seed layer deposited on a molybdenum layer. A robust Mo/Cu interface is satisfactory to prevent Kirkendall voiding but in order to further improve the interface morphology, a ratio between elements I and III is to be optimized. For example, copper (Cu) left over at the Mo/Cu interface shall be controlled. It has been identified more particularly that a minimum amount of Cu required to react with indium (In) and to form a C
  • CuInGaS(or Se) I-III-VI material can be obtained by electroplating a Culn2 alloy on a Mo/Cu interface followed by the electroplating of a CuGa2 alloy.
  • a thin Cu or In seed layer is deposited on top of the Mo in a vacuum system. Both the Mo and the seed are deposited in vacuum without exposure to air, for example by using a technique of deposition such as vapor phase deposition (or "PVD"). Samples with 600nm Mo tensile stress and 40nm Cu seed on soda lime glass have been fabricated. The cells with tensile Mo showed no loss of adhesion and 9-10% efficiency.
  • Substrates are preferably prepared prior to PVD deposition with a washer using detergent solution and multiple steps brushes. Glass is dried with an ultra pure air flow. This contamination control prevents from possible surface defects which lead to pinholes during dry deposition step.
  • the molybdenum layer is made of several molybdenum sub-layers done with same or different PVD process conditions (power, gas ratio).
  • a specific resistivity is to be optimized to ensure film stability and further CIGS or CIGSSe layers stability.
  • the minimum Cu seed thickness is set at 74nm which is twice as the electron mean path in copper. Below this value, a strong increase of the resistivity of the copper seed layer is observed. With reference to figure 3, for a slight variation of the thickness across the substrate during coating (usual coaters having a non-uniformity of 3 to 5% across the substrate), the variation of resistance sheet can be lowered by a thicker copper seed layer.
  • the uniformity of the sheet resistance of the Mo/Cu back contact is found to be better than 5%.
  • the Mo/Cu stack can be below a specific resistivity (for example 12uOhm.cm) if the Mo layer thickness is around 600nm, providing thus abilities for growing I-III layers by electro-deposition.
  • Figure 4 shows that oxidation of the copper layer is lower with a thickness of 60 or 80nm instead of 40nm. In fact, the oxidation is detected by the brightness variation of the layer.
  • the diagram of figure 4 shows that reflectance is higher after 20 minutes of exposure to atmosphere (at a temperature of 21°C, with relative humidity of 45%).
  • Mo/Cu stack is very sensitive to exposure to atmosphere when hot.
  • the temperature of the substrate when exposed to air after sputtering process during unload step has an implication on the reflectance measured on the Mo/Cu layer at a wavelength of 560nm. More particularly, as a general rule, coated substrates should not see atmosphere preferably at temperature above 70°C, as shown on figure 5.
  • Figure 6 is a SFMS analysis diagram of:
  • Mo/Cu(PVD) structure is captured by copper rather than by Mo.
  • the Mo/Cu(PVD) seed interface is almost free of oxygen.
  • Mo/Cu(electrolysis) layer has a lot of oxygen at the Cu interface exposed to air. More particularly:
  • the Cu (PVD) capping layer on Mo has about 50 times less oxygen content than in the normal Mo layer.
  • Cu capping layer protects the Mo layer from oxidation.
  • Cu oxide can be easily removed by an acidic pH solution which can be provided by most of preexisting electrolysis baths.
  • the reduced amount of oxygen atoms (i.e. oxidation) found at the interface between the adaptation layer (Mo) and the I-III-VI compound at the end of its fabrication is an evidence of the implementation of the process according to the invention.
  • the invention aims also at an electroplated I-III-VI compound layer deposited on a substrate through an adaptation layer, wherein the adaptation layer and at least one layer comprising at least elements I and III are deposited under near vacuum conditions without exposing to air said adaptation layer, and, more particularly, wherein oxidation is reduced at the interface between the adaptation layer and the I-III-VI compound layer by a factor of at least 10, compared to a structure of an electroplated I-III-VI compound layer deposited on an adaptation layer without depositing said layer comprising at least elements I and III under near vacuum conditions.
  • the invention aims also at a solar cell device comprising such an electroplated I-III-VI compound layer.
  • the adhesion between the adaptation layer and the I-III-VI compound layer passes the ISO-2409 test (vendor reference 99C8705000 test). Moreover, the interface between the I-III-VI compound layer and the adaptation layer is almost free from void.
  • the effect of such features is an improvement of the surface conductivity of the formed structure.
  • Example 1 Glass/ 600nm Mo / Cu 40nm (under vacuum)/ Cu citrate (electrolysis) / In sulfate (electrolysis) / Cu citrate (electrolysis) / In sulfate (electrolysis)
  • the Cu citrate layer is electroplated while stirring a paddle cell in the electrolysis bath, with a current density of 5 mA /cm2 during 51 seconds for growing a layer having a thickness of 110 nm.
  • the In sulfate layers are electroplated with a current density of 0,5 mA/cm2 during 1000 seconds for growing 200 nm thick layers (at 70% efficiency).
  • the second citrate Cu layer is electroplated during 70 seconds and its thickness is 150nm.
  • Example 2 Glass/600nm Mo/ 40nm Cu (under vacuum)/Cu Shipley® electrolytic solution (Layer 1) / In sulfate (Layer 2) / Cu Shipley® electrolytic solution (Layer 3) / In sulfate (Layer 4)
  • Layer 2 In sulfate, 0,5 mA/cm 2 , 1000 sec (200 nm thick at 70% efficiency), Pt anode,
  • Layer 4 In sulfate, 0,5 mA/cm 2 , 1000 sec (200 nm thick at 70% efficiency), Pt anode.
  • Example 2 is preferred to Example 1 because large grain structure of the electroplated Cu layers from the Shipley 3001 chemistry is matched with the indium chemistry, resulting in large grains in the chalcopyrite layer. Moreover, the acidity of the Shipley 3001 copper bath prevents the surface of the Cu layer deposited under vacuum from oxidation.
  • Example 3 Glass/600nm Mo/ 80nm Cu (under vacuum)/ Cu Enthone® (Layer 1) / In Enthone® (Layer 2)
  • Layer 2 In Heliofab 390, 15 mA/cm 2 , 180 sec (450 nm at 70% efficiency)
  • Example 3 is a preferred embodiment because of the efficient thickness of the copper seed layer, preventing from oxidation the interface with molybdenum, according to an advantage of the present invention. Moreover, the acidity of the Microfab SC copper bath prevents the surface of the Cu layer deposited under vacuum from oxidation.
  • Example 4 Glass/600nm Mo/ 80nm Cu (under vacuum)/ Cu Enthone® (Layer 1) / In Enthone® (Layer 2) / Ga Enthone® (Layer 3)
  • Layer 2 In Heliofab 390, 20 mA/cm2, 60 sec (380 nm)
  • Layer 3 Ga Heliofab 365, 20 mA/cm2, 15 sec (160 nm)
  • Example 4 introduces Gallium as a different element III from Indium.
  • the terms "Cu (under vacuum)" relate to copper deposition under "near vacuum conditions". Such conditions aim a monitoring of possible contamination by residual oxygen, water, etc. of the copper layer during its deposition by sputtering. More particularly, the pressure in the sputtering chambers is limited to a range between 1.10 “7 and 5.10 "6 mbar. During the sputtering process itself (of molybdenum or copper), the pressure can be higher, for example in a range form 1 to 10 ⁇ bar.
  • the deposition of the molybdenum adaptation layer is performed under near vacuum conditions (within an extended range between 1.10 “7 mbar and 10 ⁇ bar, e.g. between 10 "10 bar and 10 "5 bar) and followed by the copper layer deposition in similar conditions, and more particularly without exposure to air between the two layer depositions.
  • the seed layer can be formed of another element I, such as silver, instead of copper. It can be formed also of an element III, such as indium or aluminum or an alloy of these elements which may comprise also gallium. It may be formed, more generally, of an alloy comprising elements I and/or III.
  • the thickness of the seed layer can be chosen according to the mean free path of the material chosen for the seed layer.
  • the seed layer can be formed of an elemental layer (a pure Copper layer, or a pure Indium layer), or also of an alloy layer such as Cuin, CuGa, CuInGa, or InGa.
  • the seed layer comprises “at least” elements I and/or III. Therefore, it can include another element.
  • it can include Molybdenum (Mo).
  • the seed layer can comprise alloys such as MoCu, Moln, or MoGa.
  • the electroplated elements I and/or III can be deposited as a single I-III layer.
  • salts of element I and element III can be provided in a same electrolysis bath.
  • the substrate on which the adaptation layer is deposited can be either a glass (soda lime) substrate or a metallic substrate such as a steel sheet for example.
  • the invention applies to any adaptation layer metal that oxidizes in air (e.g. Molybdenum or any other metal).

Landscapes

  • Engineering & Computer Science (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • Physics & Mathematics (AREA)
  • General Physics & Mathematics (AREA)
  • Computer Hardware Design (AREA)
  • Microelectronics & Electronic Packaging (AREA)
  • Power Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Chemical & Material Sciences (AREA)
  • Electromagnetism (AREA)
  • Inorganic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Photovoltaic Devices (AREA)
  • Surface Treatment Of Glass (AREA)

Abstract

La présente invention porte sur un procédé pour la fabrication d'une couche mince constituée d'un alliage d'éléments des groupes I-III-VI et ayant des propriétés photovoltaïques. Le procédé selon l'invention comprend des premières étapes consistant à : a) déposer une couche d'adaptation (MO) sur un substrat (SUB) et b) déposer au moins une couche (GERME) comprenant au moins des éléments des groupes I et/ou III, sur ladite couche d'adaptation. La couche d'adaptation est déposée dans des conditions de quasi-vide et l'étape b) comprend une première opération consistant à déposer une première couche d'éléments des groupes I et/ou III, dans les mêmes conditions que le dépôt de la couche d'adaptation, sans exposition de la couche d'adaptation à de l'air.
EP11797018.6A 2010-12-27 2011-12-20 Interface améliorée entre une couche de matériau à base d'éléments des groupes i-iii-vi2 et un substrat en molybdène Active EP2666184B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
EP11797018.6A EP2666184B1 (fr) 2010-12-27 2011-12-20 Interface améliorée entre une couche de matériau à base d'éléments des groupes i-iii-vi2 et un substrat en molybdène

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
EP10306519A EP2469580A1 (fr) 2010-12-27 2010-12-27 Interface améliorée entre une couche de matériau I-III-VI2 et un substrat de molybdène
EP11797018.6A EP2666184B1 (fr) 2010-12-27 2011-12-20 Interface améliorée entre une couche de matériau à base d'éléments des groupes i-iii-vi2 et un substrat en molybdène
PCT/EP2011/073401 WO2012089558A1 (fr) 2010-12-27 2011-12-20 Interface améliorée entre une couche de matériau à base d'éléments des groupes i-iii-vi2 et un substrat en molybdène

Publications (2)

Publication Number Publication Date
EP2666184A1 true EP2666184A1 (fr) 2013-11-27
EP2666184B1 EP2666184B1 (fr) 2021-01-06

Family

ID=43899614

Family Applications (2)

Application Number Title Priority Date Filing Date
EP10306519A Withdrawn EP2469580A1 (fr) 2010-12-27 2010-12-27 Interface améliorée entre une couche de matériau I-III-VI2 et un substrat de molybdène
EP11797018.6A Active EP2666184B1 (fr) 2010-12-27 2011-12-20 Interface améliorée entre une couche de matériau à base d'éléments des groupes i-iii-vi2 et un substrat en molybdène

Family Applications Before (1)

Application Number Title Priority Date Filing Date
EP10306519A Withdrawn EP2469580A1 (fr) 2010-12-27 2010-12-27 Interface améliorée entre une couche de matériau I-III-VI2 et un substrat de molybdène

Country Status (11)

Country Link
US (1) US20130269780A1 (fr)
EP (2) EP2469580A1 (fr)
JP (1) JP2014502592A (fr)
KR (1) KR20140031190A (fr)
CN (1) CN103460337B (fr)
AU (1) AU2011351600B2 (fr)
BR (1) BR112013016541A2 (fr)
MA (1) MA34759B1 (fr)
TN (1) TN2013000258A1 (fr)
WO (1) WO2012089558A1 (fr)
ZA (1) ZA201304566B (fr)

Families Citing this family (7)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8809674B2 (en) 2012-04-25 2014-08-19 Guardian Industries Corp. Back electrode configuration for electroplated CIGS photovoltaic devices and methods of making same
US9419151B2 (en) 2012-04-25 2016-08-16 Guardian Industries Corp. High-reflectivity back contact for photovoltaic devices such as copper—indium-diselenide solar cells
US9935211B2 (en) 2012-04-25 2018-04-03 Guardian Glass, LLC Back contact structure for photovoltaic devices such as copper-indium-diselenide solar cells
US9246025B2 (en) 2012-04-25 2016-01-26 Guardian Industries Corp. Back contact for photovoltaic devices such as copper-indium-diselenide solar cells
KR101389832B1 (ko) * 2012-11-09 2014-04-30 한국과학기술연구원 구리인듐셀레늄（ｃｉｇｓ） 또는 구리아연주석황（ｃｚｔｓ）계 박막형 태양전지 및 그의 제조방법
FR3028668B1 (fr) * 2014-11-13 2016-12-30 Nexcis Procede de fabrication d'une cellule photovoltaique
US10128237B2 (en) 2016-06-24 2018-11-13 Taiwan Semiconductor Manufacturing Co., Ltd. Methods of gate replacement in semiconductor devices

Family Cites Families (16)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS6480025A (en) * 1987-09-21 1989-03-24 Hitachi Ltd Apparatus for manufacturing semiconductor
JPH0877544A (ja) * 1994-06-30 1996-03-22 Fuji Electric Co Ltd 磁気記録媒体及びその製造方法
JPH0936408A (ja) * 1995-07-25 1997-02-07 Yazaki Corp 薄膜太陽電池の製造方法及びインジウム−セレン合金の製造方法
JP3804881B2 (ja) * 1996-04-29 2006-08-02 株式会社半導体エネルギー研究所 半導体装置の作製装置および半導体装置の作製方法
WO2001078154A2 (fr) * 2000-04-10 2001-10-18 Davis, Joseph & Negley Realisation de cellules solaires a base de cigs au moyen d'un bain electrolitique tamponne
CN1151560C (zh) * 2002-03-08 2004-05-26 清华大学 一种铜铟镓硒薄膜太阳能电池及其制备方法
FR2849532B1 (fr) * 2002-12-26 2005-08-19 Electricite De France Procede de fabrication d'un compose i-iii-vi2 en couches minces, favorisant l'incorporation d'elements iii
US7736940B2 (en) * 2004-03-15 2010-06-15 Solopower, Inc. Technique and apparatus for depositing layers of semiconductors for solar cell and module fabrication
JP4676771B2 (ja) * 2004-05-20 2011-04-27 新光電気工業株式会社 化合物半導体太陽電池の製造方法
CN101094726A (zh) * 2004-11-10 2007-12-26 德斯塔尔科技公司 用于以cigs建立原位结层的热方法
EP2232576A2 (fr) * 2007-12-06 2010-09-29 Craig Leidholm Procédés et dispositifs de traitement d'une couche de précurseur dans un environnement de groupe via
DE102009011496A1 (de) * 2009-03-06 2010-09-16 Centrotherm Photovoltaics Ag Verfahren und Vorrichtung zur thermischen Umsetzung metallischer Precursorschichten in halbleitende Schichten mit Chalkogenrückgewinnung
US20100255660A1 (en) * 2009-04-07 2010-10-07 Applied Materials, Inc. Sulfurization or selenization in molten (liquid) state for the photovoltaic applications
TW201042065A (en) * 2009-05-22 2010-12-01 Ind Tech Res Inst Methods for fabricating copper indium gallium diselenide (CIGS) compound thin films
WO2011028957A2 (fr) * 2009-09-02 2011-03-10 Brent Bollman Procédés et dispositifs pour le traitement d'une couche de précurseur dans un environnement de groupe via
CN101771105A (zh) * 2009-12-01 2010-07-07 郭玉钦 连续生产线制备铜铟镓硒软体薄膜太阳能光电池的方法

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO2012089558A1 *

Also Published As

Publication number Publication date
WO2012089558A1 (fr) 2012-07-05
KR20140031190A (ko) 2014-03-12
AU2011351600A1 (en) 2013-07-04
MA34759B1 (fr) 2013-12-03
EP2469580A1 (fr) 2012-06-27
BR112013016541A2 (pt) 2016-09-27
CN103460337B (zh) 2016-09-14
TN2013000258A1 (en) 2014-11-10
EP2666184B1 (fr) 2021-01-06
CN103460337A (zh) 2013-12-18
JP2014502592A (ja) 2014-02-03
ZA201304566B (en) 2014-09-25
US20130269780A1 (en) 2013-10-17
AU2011351600B2 (en) 2015-09-17

Similar Documents

Publication Publication Date Title
EP2666184B1 (fr) Interface améliorée entre une couche de matériau à base d'éléments des groupes i-iii-vi2 et un substrat en molybdène
KR101115484B1 (ko) 태양 전지 제작용 반도체 박층의 증착을 위한 기술 및 장치
JP6096790B2 (ja) 光電池のための導電性基材
Lee et al. Fabrication of CuInS 2 films from electrodeposited Cu/In bilayers: effects of preheat treatment on their structural, photoelectrochemical and solar cell properties
KR20090014146A (ko) 박막 태양 전지 제작을 위한 전구체 막 및 화합물 층의 제조 기술 및 이에 대응하는 장치
US8066863B2 (en) Electrodeposition technique and apparatus to form selenium containing layers
TW200832732A (en) Roll-to-roll electroplating for photovoltaic film manufacturing
WO2009142308A1 (fr) Procédé de fabrication de cellule solaire à couches minces à base de séléniure d’indium et de cuivre
WO1990015445A1 (fr) Pellicules semiconductrices des groupes i-iii-vi2 utiles dans des cellules solaires
US20100140098A1 (en) Selenium containing electrodeposition solution and methods
US20140020736A1 (en) Method for producing cis-based thin film, cis-based thin film produced by the method and thin-film solar cell including the thin film
US20150059845A1 (en) Czts-based thin film solar cell and method of production of same
US8409418B2 (en) Enhanced plating chemistries and methods for preparation of group IBIIIAVIA thin film solar cell absorbers
JP4055064B2 (ja) 薄膜太陽電池の製造方法
WO2011075561A1 (fr) Chimies de plaquage d'absorbeurs pour cellules solaires en couche mince des groupes ib/iiia/via
US20120288986A1 (en) Electroplating method for depositing continuous thin layers of indium or gallium rich materials
US20140048132A1 (en) Solar cell and method of preparing the same
KR101507255B1 (ko) 광전 변환 소자 및 그것을 구비한 태양 전지
US20110005586A1 (en) Electrochemical Deposition Methods for Fabricating Group IBIIIAVIA Compound Absorber Based Solar Cells
TW201427054A (zh) 光電變換元件及其製造方法、光電變換元件的緩衝層的製造方法與太陽電池
US8883547B2 (en) Production of thin films having photovoltaic properties, comprising depositing an alternate I/III or III/I multi-layer structure and annealing said structure
KR101559539B1 (ko) 태양전지, 태양전지용 배면전극 및 그 제조방법
Başol Application of electrochemical deposition techniques to thin film solar cell processing
Yoon et al. Compensation for Cracks Formed on an Electrochemically Deposited CuInSe 2 Absorption Layer
KR102284809B1 (ko) Cis 계 박막, 이를 포함하는 태양전지 및 그 제조 방법

Legal Events

Date Code Title Description
PUAI Public reference made under article 153(3) epc to a published international application that has entered the european phase

Free format text: ORIGINAL CODE: 0009012

17P Request for examination filed

Effective date: 20130612

AK Designated contracting states

Kind code of ref document: A1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

DAX Request for extension of the european patent (deleted)
17Q First examination report despatched

Effective date: 20140512

RAP1 Party data changed (applicant data changed or rights of an application transferred)

Owner name: ELECTRICITE DE FRANCE

REG Reference to a national code

Ref country code: DE

Ref legal event code: R079

Ref document number: 602011069900

Country of ref document: DE

Free format text: PREVIOUS MAIN CLASS: H01L0021020000

Ipc: H01L0021360000

RIC1 Information provided on ipc code assigned before grant

Ipc: H01L 21/36 20060101AFI20191126BHEP

Ipc: H01L 31/032 20060101ALI20191126BHEP

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: EXAMINATION IS IN PROGRESS

GRAP Despatch of communication of intention to grant a patent

Free format text: ORIGINAL CODE: EPIDOSNIGR1

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: GRANT OF PATENT IS INTENDED

INTG Intention to grant announced

Effective date: 20200814

GRAS Grant fee paid

Free format text: ORIGINAL CODE: EPIDOSNIGR3

GRAA (expected) grant

Free format text: ORIGINAL CODE: 0009210

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: THE PATENT HAS BEEN GRANTED

AK Designated contracting states

Kind code of ref document: B1

Designated state(s): AL AT BE BG CH CY CZ DE DK EE ES FI FR GB GR HR HU IE IS IT LI LT LU LV MC MK MT NL NO PL PT RO RS SE SI SK SM TR

REG Reference to a national code

Ref country code: GB

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: AT

Ref legal event code: REF

Ref document number: 1353277

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210115

Ref country code: CH

Ref legal event code: EP

REG Reference to a national code

Ref country code: DE

Ref legal event code: R096

Ref document number: 602011069900

Country of ref document: DE

REG Reference to a national code

Ref country code: IE

Ref legal event code: FG4D

REG Reference to a national code

Ref country code: NL

Ref legal event code: MP

Effective date: 20210106

REG Reference to a national code

Ref country code: AT

Ref legal event code: MK05

Ref document number: 1353277

Country of ref document: AT

Kind code of ref document: T

Effective date: 20210106

REG Reference to a national code

Ref country code: LT

Ref legal event code: MG9D

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: GR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210407

Ref country code: HR

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: FI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: PT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210506

Ref country code: LT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: BG

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210406

Ref country code: NO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210406

Ref country code: NL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: AT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: LV

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: PL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: RS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210506

REG Reference to a national code

Ref country code: DE

Ref legal event code: R097

Ref document number: 602011069900

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SM

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: EE

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: CZ

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PLBE No opposition filed within time limit

Free format text: ORIGINAL CODE: 0009261

STAA Information on the status of an ep patent application or granted ep patent

Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: RO

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: SK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: DK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

Ref country code: ES

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

26N No opposition filed

Effective date: 20211007

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: AL

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: SI

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IT

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: IS

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210506

REG Reference to a national code

Ref country code: DE

Ref legal event code: R119

Ref document number: 602011069900

Country of ref document: DE

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MC

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

REG Reference to a national code

Ref country code: CH

Ref legal event code: PL

GBPC Gb: european patent ceased through non-payment of renewal fee

Effective date: 20211220

REG Reference to a national code

Ref country code: BE

Ref legal event code: MM

Effective date: 20211231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LU

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211220

Ref country code: IE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211220

Ref country code: GB

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211220

Ref country code: DE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20220701

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: BE

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: LI

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211231

Ref country code: CH

Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES

Effective date: 20211231

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: HU

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT; INVALID AB INITIO

Effective date: 20111220

Ref country code: CY

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106

P01 Opt-out of the competence of the unified patent court (upc) registered

Effective date: 20231024

PGFP Annual fee paid to national office [announced via postgrant information from national office to epo]

Ref country code: FR

Payment date: 20231121

Year of fee payment: 13

PG25 Lapsed in a contracting state [announced via postgrant information from national office to epo]

Ref country code: MK

Free format text: LAPSE BECAUSE OF FAILURE TO SUBMIT A TRANSLATION OF THE DESCRIPTION OR TO PAY THE FEE WITHIN THE PRESCRIBED TIME-LIMIT

Effective date: 20210106